Textile material and inhibition of acid-fading dyes thereon



United States Patent TEXTILE MATERIAL 'AND INHIBITION OF 'ACID- FADING DYES THEREON Nathaniel A. Matlin, Levittown, and Leo S. Luskin, Philadelphia, Pa., assignors to Rohm & Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application January 27, 1955 r Serial No. 484,595

' 6 Claims. (Cl. 8-61) 4 This invention relates to colorations and has as its primary object to protect colorations on textile materials produced by certain dyestulfs against change of shade due to certain chemical agencies.

It is [known that certain dyeings, which are otherwise satisfactory, undergo change of shade as a result of exposure to an atmosphere containing the combustion products of coal gas. This disadvantage is found, for example, in the case of dyeings on materials of cellulose acetate or.other ester or ether of cellulose by dyestuifs of the amino-anthraquinone series, especially 1-amino-4-hydroxyand. 1:4-diamino-anthraquinones including 1:4-diamino-anthraquinones in which one or both amino groups carry an alkyl (including hydroxy alkyl) substituent.

We have now found that dyeings which are normally unstable towards the combustion products of coal gas in the sense. of undergoing a change of shade when exposed to atmospherecontaining such products, for instance the atmospheres of rooms which have been heated or illuminated with coal gas, can be rendered more resistant to such agencies by the presence of an N-substituted aminopropionitrile having the structure of Formula I:

where R is phenyl, benzyl, cyclohexyl, or an aliphatic hydrocarbon group having at least 8 carbon atoms. The preferred compounds are those which contain no aryl ring. Of the preferred group, the most advantageous from the standpoint of cost are those in which R is a. tertiary alkyl group. They have the structure of Formula in which R, R, and R are alkyl groups having from 1 to 12 carbon atoms, the sum of the carbons in all of the groups R, R, and R being 7 to 14. Examples of the compounds include t-octylaminopropionitrile of the Formula H:

Patented May 26, 1959 ICC these improved characteristics. However, the size of the long chain aliphatic radical should not exceed 15 carbon atoms or the resistance to ordinary dry cleaning solvents will be appreciably decreased. The shorter this aliphatic radical, the greater the resistance to dry cleaning solvents, but if it becomes less than 8 carbon atoms in size, it becomes sensitive to washing.

The presence of 1% to 3% by weight of the N-substituted cyanoethylamine on the weight of the textile material is generally adequate for inhibiting gas-fading to a practical extent. The inhibitor may be introduced before, during, or after dyeing of the material. If desired, it may be incorporated in a spinning melt, solution, or dispersion, e.g., of cellulose acetate in acetone and then spun into fibers from which the textile material may be formed by weaving, knitting, etc. The dye may be present in the spinning solution or the textile material obtained from the fibers may be dyed later.

Alternatively, the inhibitor may be exhausted onto the textile material from an aqueous dispersion thereof, such as from the same aqueous bath used to apply the dye to the material either simultaneously with the inhibitor or subsequently to the application thereof. The bath ratio to textile material may vary from 20:1 to 50:1 or higher.

When the lower ratio is used, there should be present at least 0.05% by Weight of the inhibitor dispersed therein and there may be up to 0.15% or more. When a higher bath ratio is used, a correspondingly lower proportion of inhibitor may be present from 0.025% and up. Conventional amounts of dyes may be used, such as from about 0.2% to 3% by Weight of the textile material and they may be added to the aqueous bath along with the inhibitor after the textile material is introduced so that both the dye and inhibitor'are exhausted onto the textile simultaneously, or the dye and inhibitor may be separately exhausted onto the textile in either order from suitable aqueous baths thereof being added to the baths after the textile is wetted out therein. The bath temperature for applying the inhibitor may be from room temperature to about C. The dyeing baths whether they serve to apply only the dye or both the inhibitor and the dye may have the conventional temperatures of about 60 C. to 95 C.

The inhibitor, being insoluble in water, is dispersed therein by a suitable dispersing agent, such as one of nonionic type. Examples thereof are the alkylphenoxypoly ethoxyethanols in which the alkyl group has from 8 to 18' carbon atoms, such as octyl, t-octyl, dodecyl, decyl, hexa decyl, and octadecyl and there are from 8 to 20 oxyethylene units in the molecule. About 3% to 10% of the dispersing agent may be used, based on the weight of the inhibitor. 1 i g The dyes may be dispersed by suitable dispersing agents, generally of anionic type, such as soaps, including triethanolamine oleate, stearate, etc., tall oil soaps, lauryl alcohol sulfate, higher alkyl-substituted phenol sulfonates, such as t-octyl-phenol sulfonate.

The preferred inhibitors of the present invention are also characterized by a complete absence of aryl substituents which are known to have a tendency to yellow as a result of the introduction of nitro groups into aryl nuclei, such as into a benzene ring. The preferred in hibitors of the present invention have no yellowing tendencies.

In the following examples, the percentages and parts are by weight unless otherwise noted and the cycles of protection were determined by the Tentative Test Method 23-52, Technical Manual and Yearbook of the A.A.T.C.C., vol. XXX (1954), p. 87.

Example 1 A cellulose acetate fabric was introduced into, and agitated in, 20 times its weight of an aqueous dyebath maintained at 85 C. and containing 0.05% by weight (of the bath) of t-octylaminopropionitrile of Formula II above dispersed by 0.005% by weight of t-octylphenoxypolyethoxyethanol containing about oxyethylene groups and 0.02% (on the bath) of l-monomethylamino-4-(2- hydroxyethyl)amino anthraquinone dispersed by 0.02% of tn'ethanolamine oleate. After about one hour, exhaustion of dye and inhibitor was practically complete. About three cycles of protection against gas-fading were obtained, so that the inhibitor quadrupled the resistance to such fading.

Example II The procedure of Example I was repeated replacing the anthraquinone dye with Celanthrene Brilliant Blue FFS (Pr. 228). The treated fabrics showed similar resistance to gas-fading.

Example Ill The procedure of Example I was repeated replacing the compound of Formula II with the same amount of phenylaminopropionitrile with similar improvement in the resistance to gas-fading.

Example IV The procedure of Example I was repeated replacing the compound of Formula II with the same amount of benzylaminopropionitrile with similar improvement in the resistance to gas-fading.

Example V The procedure of Example I was repeated replacing the compound of Formula II with the same amount of cyclohexylaminopropionitrile with similar improvement in the resistance to gas-fading.

Example VI The procedure of Example I was repeated replacing the compound of Formula II with the same amount of 2- ethylhexylaminopropionitrile with similar improvement in the resistance to gas-fading.

Example VII A cellulose acetate fabric was dyed by introducing it into, and agitating it in, 40 times its weight of an aqueous solution maintained at 90 C. containing dispersed therein 0.012% (on the bath) of 1,4-di(monohydroxyetl1ylamino)anthraquinone dispersed by 0.012% of the sodium salt of the oleic acid amide of methyl taurine. After about an hour, dyeing was complete. The fabric was removed and dried. It was then introduced into, and agitated in, 40 times its weight of an aqueous bath at room temperature containing 0.04% (on the bath) of a mixture of fi-cyanoethylamines obtained by the addition reaction of acrylonitrile with a mixture of primary amines having alkyl groups ranging from C H to C H and having the amine nitrogen attached to tertiary carbon atoms (such reaction may be effected in the presence of aqueous acetic acid at 80 to 90 C. for about 16 hours). These fi-cyanoethylamines were dispersed by 0.004% of dodecylphenoxypolyethoxyethanol containing about 14 oxyethylene units. The fabric was then dried and found to exhibit about 3 cycles of protection against gas-fading.

Example VIII A cellulose acetate fabric dyed with Celanthrene Brilliant Blue FFS (Pr. 228) is treated in a pad with an aqueous bath containing 2.0% (on the bath) of t-octyl- .4. aminopropionitrile of Formula VIII dispersed with 0.2% (on the bath) of a t-octylphenoxypolyethoxyethanol containing about 10 oxyethylene groups. The fabric was dried at 260 F. and had picked up 1.5% of solids from the pad liquor. This treatment provided 3 cycles of protection.

In general, the dyed textile materials carrying the inhibitors of the present invention show, depending on the proportion of inhibitor used, from 2 to 4 cycles of protection against gas-fading when measured by the abovedescribed Tentative Test Method 23-52 so that their durability in this respect is tripled, quadrupled or even quintupled.

While our invention has been specifically illustrated in connection with the treatment of dyeings on cellulose acetate, dyeings on other textile materials made of or containing organic derivatives of cellulose may be treated in like manner to improve the fastness of their colorations to gas fumes, whether the dyeings are made with the dyestuifs of the foregoing examples or with other cellulose acetate dyestuffs, anthraquinone or azo, particularly those dyeing in blue shades, for instance, 1,4,5,8-tetraaminoanthraquinone, 1,4 di (monomethylamino) anthraquinone, 1 methylamino 4 (2 hydroxy-ethyl) aminoanthraquinone, 1,4 diamino 5 nitro-anthraquinone, 1- amino-4-anilidoanthraquinone, 4-(4 amino phenylazo)- nitrobenzene, 4-(2-hydroxy-4-nitrophenylazo)-N,N di-(2- hydroxyethyl) -m toluidine, 6 (2 bromo 4,6 dinitrophenylazo)-3-hydroxy-7-methyl-N secondary butyl 1,2, 3,4-tetrahydroquinoline, 4-(2,4-dinitrophenylazo) -N,N-di- (Z-hydroxyethyl)-m-toluidine, 4 (2 bromo-4,6-dinitrophenylazo)-N,N-diethyl 5 methyl-o-anisidine, and 4(2- chloro-4,6-dinitrophenylazo)-1-napl1thy1amine.

As various other embodiments of the invention will occur to those skilled in the art, it is not intended that the 'scope of the patent be limited except as is required by the prior art and the appended claims.

We claim:

1. Textile material resistant to gas-fading comprising fibers of an organic derivative of cellulose dyed with a dyestuff normally tending to fade on exposure to acid fumes and having incorporated therein a compound h'av ing the structure of formula in which R, R, and R are alkyl groups having from 1 to 12 carbon atoms, the sum of the carbons in all of the groups R, R and R being 7 to 14.

2. Textile material resistant to gas-fading comprising fibers of a cellulose ester dyed with a dyestuff normally tending to fade on exposure to acid fumes and having incorporated therein t-octylaminopropionitrile having the structure of formula 3. Textile material resistant to gas-fading comprising fibers of an organic derivative of cellulose dyed with a dyestuff normally tending to fade on exposure to acid fumes and having incorporated therein t-octylaminopropionitrile having the structure of formula as defined in claim 2.

4. Textile material resistant to gas-fading comprising fibrous cellulose acetate dyed With a dyestuff normally tending to fade on exposure to acid fumes and having incorporated therein a compound as defined in claim 1.

5. Textile material resistant to gas-fading comprising fibers of an organic derivative of cellulose dyed with an aminoanthraquinone dye and having incorporated therein from 1% to 3% by weight of a compound as defined in claim 1.

6. Textile material resistant to gas-fading comprising fibers of an organic derivative of cellulose dyed with an.

5 6 aminoanthraquinone dye and having incorporated therein 2,539,212 Strobel I an, 23, 1951 from 1% to 39? by weight of t-octylaminopropionitrile 2,813,773 Eisele Nov. 19, 1957 as defimd m clam FOREIGN PATENTS References Cited in the file of this patent 5 ,077,680 France May 5, 1954 UNITED STATES PATENTS OTHER REFERENCES 2,008,902 Ellis July 23, 1935 Br. Rayon and Silk Jour. for December 1951, pp. 63, 2,017,119 Ellis Oct. 15, 1935 64, 66. I

2,083,122 Olpin June 8, 1937 10 

1. TEXTILE MATERIAL RESISTANT TO GAS-FADING COMPRISING FIBRES OF AN ORGANIC DERIVATIVE OF CELLULOSE DYED WITH A DYESTUFF NORMALLY TENDING TO FADE ON EXPOSURE TO ACID FUMES AND HAVING INCORPORATED THEREIN A COMPOUND HAVING THE STRUCTURE OF FORMULA 